Abstract
The catalytic asymmetric α-C-H functionalization of amines features as an ideal strategy for the synthesis of advanced chiral amines from abundant prochiral amines. However, the difficulty of activating inert C-H bond and the elusive reactivity and selectivity of the carbanion intermediates limited its development. We discovered organocatalytic amine α-C-H functionalization reactions through 1,4-addition reaction. In these reactions, various primary amines including aliphatic amines and α-fluorinated amines underwent both functionalization reactions smoothly affording versatile chiral amines. These reactions were promoted by a class of powerful new organo-catalysts and enabled by new N-arylidene ligands as removable activators. The catalytic asymmetric α-C-H functionalization of nitriles was also investigated. Initial studies indicated nitriles could be activated in α-C-H functionalization reactions via organocatalysis.